DK147391B - Aqueous POLYVINYL BUTYRAL DISTRIBUTION AND USE THEREOF BY COVERING METAL SURFACES - Google Patents
Aqueous POLYVINYL BUTYRAL DISTRIBUTION AND USE THEREOF BY COVERING METAL SURFACES Download PDFInfo
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- DK147391B DK147391B DK519977AA DK519977A DK147391B DK 147391 B DK147391 B DK 147391B DK 519977A A DK519977A A DK 519977AA DK 519977 A DK519977 A DK 519977A DK 147391 B DK147391 B DK 147391B
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- polyvinyl butyral
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31688—Next to aldehyde or ketone condensation product
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Description
i 147391in 147391
Den foreliggende opfindelse angår en vandig dispersion af polyvinylbutyral til anvendelse ved overtrækning af me1i&l overflader.The present invention relates to an aqueous dispersion of polyvinyl butyral for use in coating medium surfaces.
Polyvinylacetaler udviser interessante egenskaber, når man anvender dem som overtræk, men det har hidtil været nødvendigt at anvende dem i opløsning i organiske opløsningsmidler.Polyvinyl acetals exhibit interesting properties when used as coatings, but so far it has been necessary to use them in solution in organic solvents.
Man har foreslået forskellige fremgangsmåder til opnåelse af vandige dispersioner af polyvinylacetaler. Således beskrives i fransk patentskrift nr. 1 220 859 opnåelse af polyvinylacetal-dispersioner ved i ét trin at foretage en acetalisering af polyvinylalkohol og en dispergering af den dannede acetal. Man arbejder ved temperaturer på 70 -80 °C i nærvær af sure katalysatorer, der er alkylarylsul-fonater indeholdende en højere alkylgruppe, f.eks. phenyl-cogasinsyre eller phenylsinarolsulfonsyre.Various methods have been proposed for obtaining aqueous dispersions of polyvinyl acetals. Thus, French Patent No. 1,220,859 discloses obtaining polyvinyl acetal dispersions by performing, in one step, acetalization of polyvinyl alcohol and dispersion of the acetal formed. One operates at temperatures of 70-80 ° C in the presence of acidic catalysts which are alkylarylsulfonates containing a higher alkyl group, e.g. phenylcogasic acid or phenylsinarol sulfonic acid.
Ifølge den foreliggende opfindelse tilvejebringes en vandig polyvinylbutyraldispersion med en granulometri på 0,01-5^υιη og uden indhold af plastificeringsmiddel, som er ejendommelig ved, at den er opnået ved samtidig butyralisering af en polyvinylalkoholopløsning med en blanding af butanol og en a-aldehydsyre i et vægtforhold på mellem 99/1 og 80/20, fortrinsvis 95/5 og 85/15, og dispergering af den opnåede butyral ved en temperatur, der er lavere end eller lig med 30 °C, i nærvær af et emulgeringsmiddel og i nærvær af phos-phorsyre som kondensationskatalysator.According to the present invention, there is provided an aqueous polyvinylbutyral dispersion having a granulometry of 0.01-5 µm and containing no plasticizer, which is obtained by the simultaneous butyralization of a polyvinyl alcohol solution with a mixture of butanol and an α-aldehyde acid. in a weight ratio of 99/1 to 80/20, preferably 95/5 to 85/15, and dispersing the obtained butyral at a temperature lower than or equal to 30 ° C, in the presence of an emulsifier and in presence of phosphoric acid as a condensation catalyst.
Man anvender fortrinsvis vandige polyvinylalkoholopløsnin-ger med et tørstofindhold på mellem 5 og 25?ό, fortrinsvis på mellem 10 og 20?ό.Preferably aqueous polyvinyl alcohol solutions having a solids content of between 5 and 25 [mu] m, preferably between 10 and 20 [mu] m, are used.
De anvendte polyvinylalkoholer har et estertal på under 50, svarende til en hydrolysegrad på over 96 mol%. Visko- 147391 2 siteten er i reglen lav, af størrelsesordenen 4-20 mPa' S i en 4?ό opløsning i vand ved 20 QC.The polyvinyl alcohols used have an ester number of less than 50, corresponding to a degree of hydrolysis of more than 96 mol%. The viscosity is generally low, of the order of 4-20 mPa 'S in a 4? Ό solution in water at 20 QC.
Som det aldehyd, der er nødvendigt til butyraliseringen, anvendes som nævnt en blanding af butanal og en a-aldehyd-syre i et vægtforhold på mellem 99/1 og 80/20, fortrinsvis på mellem 95/5 og 85/15. Som α-aldehydsyre anvendes fortrinsvis glyoxylsyre.As mentioned, as mentioned, as the aldehyde needed for the butyralization, a mixture of butanal and an α-aldehyde acid is used in a weight ratio of between 99/1 and 80/20, preferably between 95/5 and 85/15. As α-aldehyde acid, glyoxylic acid is preferably used.
Molforholdet mellem denne blanding og polyvinylalkoholen varierer i reglen mellem 0,7 og 1 i afhængighed af det ønskede slutprodukt.The molar ratio of this mixture to the polyvinyl alcohol generally varies between 0.7 and 1 depending on the desired final product.
Phosphorsyre er en særdeles velegnet kondensationskatalysator. Man anvender i regelen sådanne mængder, at pH i reaktionsmediet bestående af polyvinylalkoholopløsning, aldehyd, oi-aldehydsyre og emulgeringsmiddel er lavere end eller lig med 2 fortrinsvis af størrelsesordenen 1,1 - 1,5.Phosphoric acid is a particularly suitable condensation catalyst. Generally, such amounts are used so that the pH of the reaction medium consisting of polyvinyl alcohol solution, aldehyde, oaldehyde acid and emulsifier is lower than or equal to 2, preferably of the order of 1.1 to 1.5.
Man har konstateret, at anvendelsen af aldehydsyren muliggør en nedsættelse af den nødvendige phsophorsyremængde til opnåelse af den nævnte pH.It has been found that the use of the aldehyde acid enables a reduction in the amount of phsophoric acid required to achieve the said pH.
Som emulgeringsmidler anvender man kommercielt tilgængelige, fortrinsvis anioniske produkter, såsom alkalimetalsalte af mættede eller umættede langkædede fedtsyrer, al-kylarylsulfonat eller alkalimetalalkylsulfater. Man anvender betydelige mængder overfladeaktivt middel, i regelen 4-6 vægt-%, beregnet på den færdige polymer.Commercially available, preferably anionic products such as alkali metal salts of saturated or unsaturated long chain fatty acids, alkylarylsulfonate or alkali metal alkyl sulfates are used as emulsifiers. Significant amounts of surfactant are used, usually 4-6% by weight, based on the finished polymer.
De omhandlede dispersioner fremstilles på følgende måde: I en vandig opløsning af polyvinylalkohol indføres under kraftig omrøring emulgeringsmidlet og derpå aldehydblandingen, derpå katalysatoren, idet reaktionsmediet holdes ved omgivelsestemperatur 20 - 22 °C hjælp af et i sig selv kendt afkølingsorgan i'et tidsrum på 1 - 2 timer.The present dispersions are prepared as follows: Into an aqueous solution of polyvinyl alcohol, vigorously stir the emulsifier and then the aldehyde mixture, then the catalyst, keeping the reaction medium at ambient temperature from 20 to 22 ° C by means of a cooling means known per se for a period of 1 - 2 hours.
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Ued reaktionens afslutning kan man lade temperaturen stige til hen mod 30 °C for hurtigere at afslutte butyraliserin-gen.At the end of the reaction, the temperature can be raised to 30 ° C to complete the butyralization more quickly.
Fra begyndelsen af butyraliseringsreaktionen iagttager man en ændring af reaktionsmediets udseende: denne klare og flydende væske undergår en viskositetsforøgelse og bliver uigennemsigtig hvorpå den igen bliver flydende og hvid.From the beginning of the butyralization reaction, a change in the appearance of the reaction medium is observed: this clear and liquid liquid undergoes a viscosity increase and becomes opaque and then it becomes liquid and white again.
Derved dannes dispersionen: partikelstørrelsen afhænger af omrøringshastigheden og mængden af overfladeaktivt middel.The dispersion is thus formed: the particle size depends on the rate of stirring and the amount of surfactant.
De opnåede dispersioner har et tørstofindhold af størrelsesordenen 10 - 20?ό. De kan koncentreres ved fjernelse af vand ved omgivelsestemperaturen på i sig' selv kendt måde, indtil man når et tørstofindhold på 35 - 45¾.The obtained dispersions have a solids content of the order of 10 - 20? Ό. They can be concentrated by removing water at ambient temperature in a manner known per se until a solids content of 35 - 45¾ is reached.
Disse dispersioner er homogene og stabile endog ved neutralisation til pH 8 - 9. De er filmdannende ved temperaturer af størrelsesordenen 45 - 50 °C, men de kan gøres filmdannende ved omgivelsestemperaturen ved tilsætning af plasti-ficeringsmidler eller sædvanligvis til vinylpolymere anvendte koalesceringsmidler.These dispersions are homogeneous and stable even by neutralization to pH 8 - 9. They are film-forming at temperatures of the order of 45-50 ° C, but they can be made film-forming at ambient temperature by the addition of plasticizers or usually coalescing agents used for vinyl polymers.
Granulometrien af polyvinylbutyralpartiklerne er meget fin.The granulometry of the polyvinyl butyral particles is very fine.
Den varierer fra 0,01 - 5^um for partikelagglomeraterne. Middelstørrelsen er 0,05 - l^um.It ranges from 0.01 - 5 µm for the particle agglomerates. The average size is 0.05 - 1 µm.
Den opnåede polyvinylbutyral har et indhold af polyvinyl-alkoholgrupper, der i regelen er 10 - 30?ί, oftest 12 - 25¾. Indholdet af polyvinylacetatgrupper er 1 - 3¾.The polyvinyl butyral obtained has a content of polyvinyl alcohol groups, which are usually 10 - 30 µl, most often 12 - 25 µl. The content of polyvinyl acetate groups is 1 - 3¾.
Middelmolekylvægten er mellem 30 000 og 150 000.The average molecular weight is between 30 000 and 150 000.
De omhandlede dispersioner er lagringsstabile og dekanterer ikke. De kan anvendes som basis for mere komplekse midler indeholdende f.eks. tværbindingsdygtige formstoffer, 4 147391 fyldstoffer og enhver anden form for tilsætning- Påført på forskellige metalliske bærere og tørret ved en temperatur på.40 °C fører de til holdbare homogene overtræk med en god styrke.The present dispersions are storage stable and do not decant. They can be used as a basis for more complex agents containing e.g. crosslinkable resins, 4 147391 fillers and any other form of additives - Applied to various metallic carriers and dried at a temperature of.40 ° C, they lead to durable homogeneous coatings of good strength.
Anvendelsen af α-aldehydsyrer muliggør en forøgelse af vedhængningen til metalliske bærere, især efter en fugtigheds-behandling- Man konstaterede iøvrigt, at dispersionens filmdannelsestemperatur sænkedes i betragtelig grad.The use of α-aldehyde acids enables an increase in the adherence of metallic carriers, especially after a moisture treatment. It was also found that the film formation temperature of the dispersion was substantially lowered.
EKSEMPEL 1 I en reaktionsbeholder på 6 000 cm^ forsynet med en omrører af ankertypen, der drejer med 300 omdr./min., anbringes: 4 500 cm^ af en vandig 10¾ polyvinylalkoholopløsning med følgende karakteristika:EXAMPLE 1 Into a reaction vessel of 6,000 cm 2 provided with an anchor type rotator rotating at 300 rpm is placed: 4,500 cm 2 of an aqueous 10¾ polyvinyl alcohol solution having the following characteristics:
Viskositet som 4¾ vandig opløsning (20 °C): 4 mPa*S Estertal: 20 36,1 g anionisk emulgator af typen natriumlaurylsulfat, svarende til 5% af den færdige polymer.Viscosity as 4¾ aqueous solution (20 ° C): 4 mPa * S Estimate: 20 36.1 g of sodium lauryl sulfate anionic emulsifier, corresponding to 5% of the finished polymer.
Under omrøring tilsættes i løbet af nogle minutter: 302,5 cm^ butyraldehyd indeholdende 94,5¾ aldehyd. Efter homogenisering af blandingen er dens pH 5,6.With stirring, add in a few minutes: 302.5 cm 2 of butyraldehyde containing 94.5¾ aldehyde. After homogenizing the mixture, its pH is 5.6.
Man tilsætter 27,2 g glyoxylsyre og derpå 10 cm^ 75¾ phos-phorsyre. Blandingens pH er derpå 1,2.27.2 g of glyoxylic acid are added and then 10 cm 2 of 75¾ phosphoric acid. The pH of the mixture is then 1.2.
I en time holdes et omgivende vandbad på 20 °C, idet blandingens temperatur svinger mellem 20 og 23 °C uden kalorietilførsel, da reaktionen er exotherm. Man bemærker under denne første time, nærmere bestemt mellem 15 5 147391 og 30 minutter efter sammenblandingen, en ændring af blandingens udseende. Denne viser sig ved en forøgelse og derpå en nedgang af viskositeten. Det er i dette tidsrum, at dispersionen dannes, og partiklerne antager deres definitive størrelse.For one hour, an ambient water bath of 20 ° C is maintained, with the temperature of the mixture fluctuating between 20 and 23 ° C without caloric feed, as the reaction is exothermic. During this first hour, more specifically, between 15 minutes and 30 minutes after mixing, a change in the appearance of the mixture is noticed. This is shown by an increase and then a decrease in viscosity. It is during this time that the dispersion is formed and the particles assume their final size.
Man afslutter butyraliseringen ved at opvarme den opnåede emulsion til 30 °C i to timer, hvorpå man afkøler til 25 °C.The butyralization is completed by heating the obtained emulsion to 30 ° C for two hours, then cooling to 25 ° C.
Den opnåede dispersion har følgende karakteristika: pH 1,2 residual butanal 0,2¾ (forbliver stabil over tiden) tørstof 15¾The dispersion obtained has the following characteristics: pH 1.2 residual butanal 0.2¾ (remains stable over time) dry matter 15¾
Brookfield viskositet ved 23 °C og 50Brookfield viscosity at 23 ° C and 50 ° C
omdr./minut ca..· 15 mPa·Srpm approx .. · 15 mPa · S
partikeldimension 0,1-l^umparticle size 0.1-1 µm
Den polymere har selv følgende karakteristika: viskositet af en polymer- opløsning i 95¾ etha-The polymer itself has the following characteristics: viscosity of a 95¾ ethanol polymer solution.
nol ved 20 °C 10 mPa*Snol at 20 ° C 10 mPa * S
vægt-?i polyvinyl-qlkpholgrupper ca. 18,5by weight in polyvinyl-glycol groups approx. 18.5
Dispersionen påføres på stålplader. Man afsætter fire successive lag ved at anbringe stålplader i en centrifuge sammen med dispersionen og ved at tørre hvert lag i tre minutter ved 140 °C. Man opnår et færdigt overtræk på ca.The dispersion is applied to steel plates. Four successive layers are deposited by placing steel plates in a centrifuge with the dispersion and by drying each layer for three minutes at 140 ° C. A finished coating of approx.
20^um, der er ekstremt adhererende ved prøven ved kredsning med en kam (norm NF T 30 038) og har en god smidighed ved stansningsprøven efter Erichsen (norm NF T 30 019).20 µm, which is extremely adherent to the sample by combing with a comb (norm NF T 30 038) and has good flexibility in the punching test after Erichsen (norm NF T 30 019).
Dette overtræk er holdbart i mere end 300 timer ved prøven for modstandsdygtigheden mod salttåge (norm NF X 41 002) uden tilsynekomst iaf rust. Endelig bevarer den en fremragende vedhængen til bæreren.This coating is durable for more than 300 hours in the test for resistance to salt mist (norm NF X 41 002) without appearance of rust. Finally, it retains an excellent attachment to the wearer.
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Filmdannelsestemperaturen er sænket til 45 °C.The film formation temperature is lowered to 45 ° C.
EKSEMPEL 2 I en 6 000 cm^ reaktionsbeholder· forsynet med ankeromrører, der drejer med 300 omdr./min., anbringes: 4 500 cm^ af en 10% polyvinylalkoholopløsning med følgende karakteristika:EXAMPLE 2 In a 6,000 cm 2 reaction vessel · fitted with 300 rpm anchor stirrer, place: 4,500 cm 2 of a 10% polyvinyl alcohol solution having the following characteristics:
Viskositet af 4% vandig opløsning ved 20 °C: mPa*S Estertal: 20 43,70 g anionisk emulgator af typen natriumlaurylsulfat, svarende til 6% af den færdige polymer.Viscosity of 4% aqueous solution at 20 ° C: mPa * S Estimate: 20 43.70 g of sodium lauryl sulfate anionic emulsifier, corresponding to 6% of the finished polymer.
Under omrøring tilsættes i løbet af nogle minutter: 336 cm^ butyraldehyd indeholdende 94,5% aldehyd. Efter homogenisering er blandingens pH 5,6.While stirring, add in a few minutes: 336 cm 2 of butyraldehyde containing 94.5% aldehyde. After homogenization, the pH of the mixture is 5.6.
Man tilsætter herpå 20 cm^ 75% phosphorsyre, hvorpå blandingens pH indstiller sig til 1,2.20 cm 3 of 75% phosphoric acid is then added and the pH of the mixture adjusted to 1.2.
I en time holdes det omgivende vandbad på 20 °C, det blandingens temperatur svinger mellem 20 og 23 °C uden kalorietilførsel, da reaktionen er exotherm.For one hour, the ambient water bath is kept at 20 ° C, the temperature of the mixture fluctuates between 20 and 23 ° C without caloric feed as the reaction is exothermic.
Man bemærker i løbet af denne første time, nærmere bestemt i tidsrummet mellem 15 og 30 minutter efter sammenblanding, en ændring af blandingens udseende. Dette viser sig ved en forøgelse og derpå en nedgang af viskositeten. Det er i dette tidsrum at dispersionen dannes og partiklerne antager deres definitive størrelse.During this first hour, more specifically in the period between 15 and 30 minutes after mixing, a change in the appearance of the mixture is noticed. This is shown by an increase and then a decrease in viscosity. It is during this time that the dispersion is formed and the particles assume their final size.
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Man afslutter butyraliseringen ved at opvarme den opnåede emulsion til 30 °C i to timer, hvorpå man afkøler til 25 °C.The butyralization is completed by heating the obtained emulsion to 30 ° C for two hours, then cooling to 25 ° C.
Den opnåede dispersion har følgende karakteristika: pH 1-2 residual butanal 0,2¾ (forbliver stabil over tiden) tørstof 15¾The obtained dispersion has the following characteristics: pH 1-2 residual butanal 0.2¾ (remains stable over time) dry matter 15¾
Brookfield viskositet ved 23 °C og 50Brookfield viscosity at 23 ° C and 50 ° C
omdr./minut 10-20 mPa*Srpm 10-20 mPa * S
partikeldimension 0,1-l^umparticle size 0.1-1 µm
Den opnåede polymer har følgende karakteristika: viskositet af en polymer- opløsning i 95¾ ethanolThe polymer obtained has the following characteristics: viscosity of a polymer solution in 95¾ ethanol
ved 20 °C 9,5-10,5 mPa’Sat 20 ° C 9.5-10.5 mPa'S
vægt-“0 polyvinyl-alkoholgrupper 17,5-20,5weight of "0 polyvinyl alcohol groups 17.5-20.5
Dispersionen påføres på stålplader. Man afsætter fire successive lag ved at anbringe stålpladerne i en centrifuge sammen med dispersionen, idet man tørrer hvert lag i tre minutter ved 140 °C.The dispersion is applied to steel plates. Four successive layers are deposited by placing the steel plates in a centrifuge with the dispersion, drying each layer for three minutes at 140 ° C.
Man opnår et færdigt overtræk med en tykkelse på ca. 20 ^um som er extremt vedhæftende ved prøven med skrabning med en kam (norm NF T 30 038) og udviser en god smidighed ved stansningsprøven efter Erichsen (norm NF T 30 019).A finished coating with a thickness of approx. 20 µm which is extremely adherent to the scraping test with a comb (norm NF T 30 038) and exhibits good agility in the punching test after Erichsen (norm NF T 30 019).
Dette overtræk er holdbart i mere end 300 timer ved prøven for bestandighed mod salttåger (norm NF x 41 002) uden forekomst af rust.This coating is durable for more than 300 hours in the test for salt mist resistance (norm NF x 41 002) without the presence of rust.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7636147 | 1976-11-24 | ||
| FR7636147A FR2372179A1 (en) | 1976-11-24 | 1976-11-24 | Polyvinyl butyral aq. dispersion prepn. - by butyralisation of polyvinyl alcohol solns. with butanal and glyoxalic acid used for coating metals |
| FR7710493A FR2385743A2 (en) | 1977-03-31 | 1977-03-31 | Polyvinyl butyral aq. dispersion prepn. - by butyralisation of polyvinyl alcohol solns. with butanal and glyoxalic acid used for coating metals |
| FR7710493 | 1977-03-31 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK519977A DK519977A (en) | 1978-05-25 |
| DK147391B true DK147391B (en) | 1984-07-16 |
| DK147391C DK147391C (en) | 1985-02-04 |
Family
ID=26219729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK519977A DK147391C (en) | 1976-11-24 | 1977-11-23 | Aqueous POLYVINYL BUTYRAL DISTRIBUTION AND USE THEREOF BY COVERING METAL SURFACES |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US4210564A (en) |
| JP (1) | JPS5365390A (en) |
| BR (1) | BR7707781A (en) |
| CA (1) | CA1093723A (en) |
| CH (1) | CH623832A5 (en) |
| DE (1) | DE2752054A1 (en) |
| DK (1) | DK147391C (en) |
| ES (1) | ES464402A1 (en) |
| GB (1) | GB1595476A (en) |
| IT (1) | IT1087937B (en) |
| LU (1) | LU78564A1 (en) |
| NL (1) | NL7712922A (en) |
| NO (1) | NO150209C (en) |
| SE (1) | SE424330B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6112334A (en) * | 1984-06-29 | 1986-01-20 | 川崎製鉄株式会社 | Composite type vibration-damping laminate |
| AU631369B2 (en) * | 1988-08-09 | 1992-11-26 | Neil Alexander North | Protective coating for an electrical or electronic circuit |
| US4968744A (en) * | 1988-11-07 | 1990-11-06 | Monsanto Company | Polyvinyl butyral polyblend |
| DE19515967A1 (en) * | 1995-05-02 | 1996-11-07 | Hoechst Ag | Anionically stabilized, aqueous polyvinylbutyral dispersions, process for their preparation and their use |
| US5534381A (en) * | 1995-07-06 | 1996-07-09 | Minnesota Mining And Manufacturing Company | Acetal polymers useful in photosensitive compositions |
| DE19640731A1 (en) * | 1996-10-02 | 1998-04-16 | Clariant Gmbh | Aqueous polyvinyl acetal dispersions |
| AT407252B (en) | 1999-05-27 | 2001-02-26 | Vianova Kunstharz Ag | AQUEOUS CORROSION PROTECTION PRIMERS BASED ON POLYVINYLBUTYRAL |
| DE10143190A1 (en) * | 2001-09-04 | 2003-03-20 | Kuraray Specialities Europe | High molecular weight, cross-linked polyvinyl butyrals, processes for their production and their use |
| US7511096B2 (en) * | 2003-01-09 | 2009-03-31 | Kuraray Europe Gmbh | Crosslinked polyvinyl acetals |
| FI118183B (en) * | 2003-05-16 | 2007-08-15 | Ciba Sc Holding Ag | A component useful in papermaking and its use |
| DE10327517A1 (en) * | 2003-06-17 | 2005-01-13 | Ht Troplast Ag | Ion-conducting thermoplastic compositions for electrochromic glazings |
| EP3587106A1 (en) * | 2018-06-26 | 2020-01-01 | Aquaspersions Ltd. | Plasticiser-free polyvinyl butyral dispersion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1069385B (en) | 1957-12-21 | 1959-11-19 | Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius S. Bruning, Firankfuirt/M | Process for the production of polyvinyl acetal dispersions |
| US3234161A (en) * | 1960-07-25 | 1966-02-08 | Monsanto Co | Preparation of stable polyvinyl acetal dispersions |
| DE1247663C2 (en) * | 1961-02-24 | 1975-11-27 | E.I. Du Pont De Nemours And Company, Wilmington, Del. (V.St.A.) | METHOD FOR MANUFACTURING POLYVINYL ACETALS |
| JPS4990792A (en) * | 1972-12-30 | 1974-08-29 |
-
1977
- 1977-11-15 US US05/851,768 patent/US4210564A/en not_active Expired - Lifetime
- 1977-11-21 JP JP13901477A patent/JPS5365390A/en active Granted
- 1977-11-22 LU LU7778564A patent/LU78564A1/xx unknown
- 1977-11-22 CA CA291,471A patent/CA1093723A/en not_active Expired
- 1977-11-22 NO NO773997A patent/NO150209C/en unknown
- 1977-11-22 GB GB48636/77A patent/GB1595476A/en not_active Expired
- 1977-11-22 DE DE19772752054 patent/DE2752054A1/en active Pending
- 1977-11-23 BR BR7707781A patent/BR7707781A/en unknown
- 1977-11-23 CH CH1435177A patent/CH623832A5/fr not_active IP Right Cessation
- 1977-11-23 NL NL7712922A patent/NL7712922A/en not_active Application Discontinuation
- 1977-11-23 ES ES464402A patent/ES464402A1/en not_active Expired
- 1977-11-23 SE SE7713256A patent/SE424330B/en not_active IP Right Cessation
- 1977-11-23 DK DK519977A patent/DK147391C/en active
- 1977-11-24 IT IT3001477A patent/IT1087937B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5639801B2 (en) | 1981-09-16 |
| GB1595476A (en) | 1981-08-12 |
| SE7713256L (en) | 1978-05-25 |
| NO773997L (en) | 1978-05-25 |
| US4210564A (en) | 1980-07-01 |
| NO150209C (en) | 1984-09-05 |
| DK519977A (en) | 1978-05-25 |
| ES464402A1 (en) | 1978-09-01 |
| CH623832A5 (en) | 1981-06-30 |
| DK147391C (en) | 1985-02-04 |
| IT1087937B (en) | 1985-06-04 |
| SE424330B (en) | 1982-07-12 |
| CA1093723A (en) | 1981-01-13 |
| LU78564A1 (en) | 1979-02-02 |
| DE2752054A1 (en) | 1978-06-01 |
| NO150209B (en) | 1984-05-28 |
| JPS5365390A (en) | 1978-06-10 |
| BR7707781A (en) | 1978-06-13 |
| NL7712922A (en) | 1978-05-26 |
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